In this paper, we report the circular dichroism (CD) spectra of two types of LH2-only mutants of Rhodobacter sphaeroides. In the first, only the wild type LH2 is present, while i the second, the B800 binding site of LH2 has been either destabilized or removed. For the first time, we have identified a band in the CD spectrum of LH2, located at approximately 780 nm, that can be ascribed to the high exciton component of the B850 band. The experimental spectra have been modeled by theoretical calculations. On this basis, the average interaction strength between the monomers in the B850 ring can be estimated to be approximately 300 cm-1. In addition, we suggest that in LH2 of Rb. sphaeroides the angles made by the Qy transitions of the B850 BChls with respect to the plane of the ring are slightly different from those calculated from the crystal structure of the Rhodopseudomonas acidophila LH2 complex.
The published crystal structure of the LH2 complex of Rhodopseudomonas acidophila is used to calculate absorption and CD spectra of this system. An important parameter, the zero crossing of the CD spectrum with respect to the absorption maximum, is shown to be sensitive to structural changes. The changes in spectral properties as a function of varying excited state energy, variation in the dielectric properties of the surrounding medium, and changes in relative orientations of the chromophores are also investigated. It is shown that the experimentally observed red shift of the zero crossing can be explained by lifting the degeneracy of the excited state of the monomers and taking into account more than half of the LH2 ring.
In this paper the circular dichroism and absorption spectra of the LH2 complex of Rhodopseudomonas acidophila, for which the atomic structure is known, are analyzed. We show that an analysis based on the distribution of the excitations in real space, and their correlations, to unravel the relation between the atomic structure of the light-harvesting complex and its excitonic properties, is particularly successful. Starting from molecular expressions for the linear susceptibility, we demonstrate that linear spectra can be viewed as originating from the product of coherence correlation functions and geometric structure factors. Effects of homogeneous and inhomogeneous broadening can be incorporated in a natural way and lead to a definition of exciton length as the distance over which coherence correlation functions decay.
The origin of the nonconservative nature of the circular dichroism (CD) spectrum of bacteriochlorophyll dimers is investigated. It is shown that coupling between the Qy and Qx transitions can, under rather restricting circumstances, lead to an asymmetrical CD spectrum: only for a limited set of relative orientations of the monomers within the dimer is the spectrum found to be asymmetrical. The relation between intensity and asymmetry of the CD spectrum is elucidated. The results are applied to the B820 subunit of the LH1 antenna system and subsequently to the antenna system LH1 itself. Differences in the geometry of the BChls in LH1 versus the LH2 structure are discussed.
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